Complex copper compounds of disazo



UNITED STATES PATENT OFFICE COMPLEX COPPER COMPOUNDS OF DISAZO DYESTUFFS Fritz Kehrerand Walter Wehrli, Basel, Switzerland, assignors to Sandoz A. G., Basel, Switzerland, a Swiss firm No Drawing. Application May 23, 1951, Serial No. 227,934. In Switzerland May 26, 1950 4 Claims- (Cl. 260-148) The present invention relates to complex copper compounds of disazo dyestuffs.

An important consideration in the preparation of new dyestufis which are to be applied to the fiber to be dyed from the dyebath, is their capacity for drawing onto the said fiber. Maximum exhaustion from the dye'bath is a manifest desideratum from the standpoint oi the econom value of the dyestufis.

A primary object of the present invention is t provide disazo dyes which, in; additi n t ot valuable properties such as the production of vivid shades of good fastness to light, are characterized by a very good drawing or exhausting wherein X stands for hydrogen or methyl, Y

capacity-parti,cularly onto cotton and regenerated cellulose fibers-whereby substantially complete exhaustion of the dyebaths may be attained.

H035 NH. ALIEN 0311 i. e. the symmetrical urea of Z-amino-S-hydroxynaphthalene-'l-sulfonic acid, on the one hand with the diazo compound from 1 mol of an aminobenzene-sulfonic acid of the formula wherein R. stands for hydro en or methyl, and on the other hand with 1 mol of a diazotized aminobenzene sulfonic acid amide derivative of the formula "very good drawing capacity,

5 colored Shades of very stands for hydrogen or alkyl, and Z stands for hydrogen, alkyl, phenyl or substituted phenyl the couplings being efiected in either order of succession-and then treating the obtained disazo dyestufi' with a copper-yielding agent,

The resultant products are the complex copper mpounds of the dyestuffs oi the formula wherein R, X, Y and Z have the previouslyrecited significances.

More specifically, the new cupriferous dyestuffs are prepared (a) by first preparing the monoazodyestufi from 1 mol of the diazotized aminobenzene-sulfonic acid derivative and 1 mol of the symmetrical urea of 2-amino-5-hydroxynaphthalene-'T-sulfonic acid and coupling this with 1 mol of a diazotized aminobenzene-sulfonic acid amide derivative, or (b) first preparing the monoazo dyestufi from 1 mol of the diazotized aminobenzene-sulfonic acid amide derivative and 1 mol of the symmetrical urea of 2-amino-5- hydroxynaphthalene-7-su1fonic acid and coupling this with 1 mol of the diazotized aminobenzene-sulfonic acid derivative, and then sub! jectin the disazo dyestuif obtained in either of these two ways to after-coppering in known manner. If the uncop-pered disazo dyestufis contain methoxy groups in ortho-positions to the azo bridges, the conversion into the complex copper compounds is enacted according to known methods wherein the methoxy groups are split during the metallization.

The new dyestufis, as afore-indicated, are characterized, in addition to good solubility, by and dye cotton and regenerated cellulose fibers in bright Bordeauxgood fastness to light.

Aminobenzene-sulfonic acids which are used in preparing the said cupriferous disazo dyestuiis, according to this invention, are the l-hydroxy- 2-aminobenzene-4-sulfonic acid and the l-methoxy-2-aminobenzenei-sulfonic acid. Aminobenzene-sulfonic acid amide derivatives which are used are, among others,

1 hydroxy 2 aminobenzene 4 sulfonic acid amide,

1 hydroxy 2 aminobenzene 4 sulfonic methylamide,

1 hydroxy 2 aminobenzene 4 sulfonic ethylamide,

1 hydroxy 2 aminobenzene 4 sulionic propylamide,

1 hydroxy 2 aminobenzene 4 sulfonic dimethylamide, v

1 hydroxy 2 aminobenzene 4 sulfonic diethylamide,

1 hydroxy 2 aminobenzene 4 sulfonic methylethylamide,

1 hydroxy 2 aminobenzene 4 sulfonic anilide,

1 hydroxy 2 aminobenzene-4-sulfonic acid- N -methyl-anilide,

1 hydroxy 2 aminobenzene-4-sulfonic acid- N-ethyl-anilide, V

1 hydroxy 2 aminobenzene-d-sulfonic acid- 4'-methyl-anilide,

1 hydroxy 2 aminobenzenei-sulfonic acid- 2'-methoXy-anilide,

1 hydroxy 2 aminobenzene-4-sulfonic acid- 3'-chloro-ani1ine, etc.

acid

acid

acid

acid

acid

acid

acid

and the corresponding l-methoxy-Z-amincbehzenel-sulfonic acid amide derivatives.

The following examples further illustrate the invention, the parts being parts by weight unless otherwise indicated. The term soda refers to sodium carbonate.

Example 1 The diazo dyestufi, which corresponds to the to formula t-ained according to Example 1.

4 terials in bright Bordeaux-colored shades of very good fastness to light.

Example 2 10 pletion of the formation of the mon'o-azo dyestufi,

the latter is reacted in soda-alkaline medium with the diazo compound of 18.9 parts of l-hydroxy-2-aminobenzene-4-su1fonic acid. The isolated disazo dyestufi is identical with that ob- It is converted into the identical complex copper compound described in Example 1, in the manner therein set forth.

' Example 3 The same cupriferous dis-azo dyestufi as that obtained according to Examples 1 and 2 can be obtained by replacing the diazo components set forth in these examples by equivalent quantities of:

1-methoxy-2-aminobenzenei-sulfonic acid and 1-methoxy-2-aminobenzene-4-sulfonic acid anilide, or 1-hydroxy-2-aminobenzene-4-sulfonic acid and 30 1-methoxy-2-aminobenzene-4-sulfonic acid anilide, or 1-methoxy-2-aminobenzene-4-sulfonic acid and 1-hydroxy-2--aminobenzene-4-sulfonic acid anilide, while otherwise proceeding'a-s described in the said examples, and then subjecting the thus-obtained disazo dyestufi to a demethylating coppering treatment with ammoniacal copper oxide according to the coppering method described in U. S. Patent 2,529,527, Example 1.

The conversion into the complex copper compound of the diazo dyestuff can, moreover, be accomplished by any of the known methods of metallization with concomitant splitting off the methoxy group or groups, as is well known in this art.

. Example 4 29.2 parts of 1-hydroxy-2-aminobenzene-4-sulionic acid-N-ethyl anilide are diazotized and coupled with 50.4 partsof the symmetrical urea OH on on on 9 H08 NRELHN- 808E i 03H OINHO hausting the dyebath, and dyes these textile ma- OCH:

of 2-amino 5 hydroxynaphthalene-I-sulionic acid in the presence of sodium bicarbonate. Upon completion of the formation of the monoazo dyestuff, the latter is coupled in-soda-alkaline 5 medium with the diazo compound from 20.8 parts of 1-methoxy-2-aminobenzene-4-sulfonic acid. The 'disazo dyestuii, which corresponds to the formula f 6 is isolated and converted into the corresponding properties are obtained by replacing the amino-- complex copper compound by treatment with ambenzene-sulfonic acid amide derivative used in maniacal copper oxide. The thus-obtained cu- Examples 1 and 2 by any one of the following,

priferous dyestufi draws very well onto cotton and otherwise proceeding accordingto the preand regenerated cellulose fibers, substantially 5 scriptions set forth in either of the said completely exhausting the dyeb-ath, and dyes examples:

these textile materials in bright Bondeaux- (a) as "ig y dxy m d colored shades of very good fastness to light. 7 lf i acid amide, or

Z Y (b) 20.2 parts of 1-hydroxy-2-aminobenzene-4- Emmp e 5 sulfonic acid methylamide, or Parts Of 1-meth0Xy-2-amlnobenzene-4' (c) 21.6 parts of l-hydroxy-2aminobenzenelsulfonic acid are diazotized and then coupled sulfomc acid ethylamide or with 50.4 parts of the symmetrical urea of 2- (d) 23 parts f 1hydrgxy-2-aminobemene 4- amino-5hydroxynaphthalene-7sulfonic acid in sulfo i a id ropylamideor the presence of sodium bicarbonate. After com- (e) 2 arts of 1 -hydroxy-2-aminobenzene-4- pletion of the formation of the monoazo dyestufi, 4 sulfonic acid dimethylamide, or it is coupled in soda-alkaline medium with the I (f) 24.4 parts of l-hydroxy-2 aminobenzeneldiazo compound from 20.2 parts of l-methoxysulfonic acid diethylamide, or 2-aminobenzene-4-su1f0nic acid amide. The dis- (g) 23.0 parts of l-hydroxy-z-aminobenzene-4- azo dyestufi, which corresponds to the formula sulfonic acid methylethylamide,

([)OH3 CIJH (IJH OCHa N=N- N=N HOaS- NH.("}.HN SOaH Hoes SQZNH: is isolated and converted into the corresponding (h) 27.8 parts of lhydroxy-2-aminobenzene-4- complex copper compound by treatment with amsulfonic acid-N-methyl-anilide, or moni-acal copper oxide. The thus-obtained cu- (2') 27.8 parts of 1hydroxy-Z-aminobenzene-4- priferous dyestuff draws very well onto cotton sulfonic acid- -methyl-anilide, or and regenerated cellulose fibers, substantially (7') 29.4 parts of l-hydroxy-2-aminobenzene4- completely exhausting the dyebath, and dyes sulfonic acid-2methoxy-anilide, orthese textile materials in bright Bordeaux- 29.9 parts of 1-hydroxy-2-amincb n -4- colored shades of very good fastness to light. su fonic acid-3'-chloro-anilide.

Exam 1e 6 The formulae of the unmetallized disazo dyep stuiis of representative members of this example Cupriferous disazo dyestufifs with similar are as follows:v

OH OH on 011 on OH N=N N=N I? Hols NH.C.HN S0311 03H O2NH CHa OCH:

N=N N= t HOaS- N'H.O.HN 50,11 01 03H 091116 Example 7 Cupriferous disazo dyestuffs with similar properties are obtained by replacing the aminobenzene-sulfonic acid amide derivative used in Example 4 or Example 5 by any one of the fol- 5 (Z) 21.6 parts of l-methoxy-Z-aminobenzene-4- 4 sulfonic acid methylamide, or

(m) 23.0 parts of l-methoxy-2-aminobenzene-4- sulfonic acid ethylamide, or

(n) 24.4 parts of 1-methoxy-2-aminobenzene-4- sulfonic acid propylamide, or

30 (-p) 25.8 parts of 1-methoxy-2-aminobenzene-4- sulfonic acid diethylamide, or

((1) 24.4 parts of 1meth0xy-2-aminobenzene-4- sulfonic acid methylethylamide, or r (r) 29.2 parts of 1-methoxy-2-aminobenzene-4- sulfonic acid-N-methyl-anilide, or

(s) 30.6 parts of 1-methoxy-2-aminobenzene-4 sulfonic acid-N-ethyl-anilide, or

(t) 29.2 parts of 1meth0xy-2-aminobenzene-4- sulfonic acid-4-methy1-anilide, or

0 (a) 30.8 parts of 1-methoxy-2-aminobenzene-4 sulfonic acid-2-methoxy-anilide, or (v) 31.3 parts of 1-methoxy-2-aminobenzene-4- sulfonic acid-3'-ch1oro-anilide.

The formulae of the unmetallized diazo dye- (0) 23.0 parts of 1-methoxy-2-aminobenzene-4- 45 stufis of representative members of this example sulfonic acid dimethylamide, or

are as follows:

Hois- N=N o t NB. .HN S0311 02-NHO0H:

100 parts of well wetted cotton are entered OCHs OCHB

OCHa

at 60 G. into a dye-bath containing in 3000 parts of water 0.5 part of the dyestuff described in Example 5 and parts of Glaubers salt. The temperature is raised to the boil within of an hour, and then 10 parts of Glaubers salt are added. The dye-bath is kept boiling during minutes. After the further addition of 10 parts of Glaubers salt the bath is allowed to cool to about 50 C. The cotton is then well rinsed and dried. It is dyed in a bright Bordeaux-colored shade of very good fastness to light.

l. A complex copper compound of a disazo dyestufi corresponding to the formula in which R and X each stands for a member selected from the group consisting of hydrogen and methyl, Y stands for a member selected from the group consisting of hydrogen and lower alkyl, and Z stands for a member selected from the group consisting OI" hydrogen, lower alkyl and mono-nuclear aryl.

2. The complex copper compound of the disazo dyestufi corresponding to the formula 3. The complex copper compound of the disazo dyestufi corresponding to the formula 0 CH3 0H OH on N=N N=N u 1103s NILCJIN SOaH sore oil -O zHg Having thus disclosed the invention, what is claimed is:

4. The complex copper compound of the disazo dyestuff corresponding to the formula 0 CH3 OH OH O CH:

l? H03 NH.C.HN 503E 08H SOQNH:

FRITZ KEHRER. WALTER WEHRLI.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,467,621 Kaiser et a1 Apr. 19, 1949 2,538,568 Kaiser et a1. Jan. 16, 1951 

1. A COMPLEX COPPER COMPOUND OF A DISAZO DYESTUFF CORRESPONDING TO THE FORMULA 